Styrylaza vinyl esters

ABSTRACT

Vinyl ester resins of substituted epoxidized hydroxystyrylaza compounds are disclosed. These vinyl esters may be combined with various reactive monomers, prepolymers or polymers and cured to give a combination of high mechanical strength and glass transition temperature.

CROSS-REFERENCE TO RELATED APPLICATION

This is a divisional of application Ser. No. 101,047, filed Sept. 25,1987, now U.S. Pat. No. 4,851,483.

BACKGROUND OF THE INVENTION

The present invention provides novel vinyl esters of epoxidizedhydroxystyrylaza compounds, as well as cured compositions prepared fromsaid vinyl esters.

Vinyl esters are the reaction product of about equivalent amounts of amonounsaturated monocarboxylic acid and a polyepoxide. One class ofvinyl esters is described in U.S. Pat. No. 3,367,992 where dicarboxylicacid half esters of hydroxyalkyl acrylates or methacrylates are reactedwith polyepoxide resins. Bowen in U.S. Pat. Nos. 3,066,112 and 3,179,623describes the preparation of vinyl esters from monocarboxylic acids suchas acrylic and methacrylic acid. Bowen also describes alternate methodsof preparation wherein a glycidyl methacrylate or acrylate is reactedwith the sodium salt of a dihydric phenol such as bisphenol A. Vinylester resins based on epoxy novolac resins are described in U.S. Pat.No. 3,301,743 to Fekete et al. Fekete et al in U.S. Pat. No. 3,256,226decribe vinyl esters where the molecular weight of the polyepoxide isincreased by reacting a dicarboxylic acid with the polyepoxide resin aswell as acrylic acid, etc. Other functional compounds containing a groupwhich is reactive with an epoxide group, such as an amine, mercaptan andthe like, may be utilized in place of the dicarboxylic acid. All of theabove-described compositions, which contain the characteristic linkages##STR1## and terminal polymerizable vinylidene groups are classified asvinyl esters.

The vinyl ester is typically combined with a reactive, dilutent: acopolymerizable vinyl monomer, to alter the viscosity of the mixture, tovary the properties of the cured coating, or for other known reasons.Most any vinyl monomer may be employed which is copolymerizable with theunsaturated groups of the vinyl ester. Such monomers include bothmonovinyl and polyvinyl monomers. Typical monomers include the alkenylaromatic monomers such as styrene, vinyltoluene, t-butylstyrene and thelike; and alkyl and hydroxyalkyl esters of acrylic and methacrylic acidsuch as methyl, ethyl, propyl, butyl, cyclohexyl and hydroxyethyl,hydroxypropyl and hydroxybutyl acrylates and methacrylates. In additionto the above, other monomers are especially useful for ultraviolet lightcurable systems such as 2-acetoxyalkyl acrylates; pentaerythritol di-,tri- or tetra- acrylate and the like may be added in any order.

The vinyl ester and copolymerizable vinyl monomer blend is acrosslinkable vinyl ester resin which is cured by mixing in a freeradical forming catalyst in an amount ranging from 0.1 to about 5percent by weight, preferably 1 to 2 percent by weight. Examples ofthese catalysts are benzoyl peroxide, tertiary butyl hydroperoxide,methylethylketone peroxide and the like. It is frequently of value toadd an accelerator such as N,N-dimethylaniline, cobalt naphthenate andthe like.

Preparation of epoxidized substituted hydroxystyrylaza compounds istaught by Ser. No. 07/317,267 filed on the same date as the instantcase. The process of this invention uses a substituted hydroxystyrylazacompound described by U.S. Pat. No. 4,600,767 which is incorporatedherein by reference. Expoxidation of the hydroxystyrylaza compound iscompleted in a conventional manner by reaction with an epihalohydrinwith subsequent dehydrohalogenation with a basic-acting material andfinally recovering the resultant styrylaza functional glycidyl etherproduct.

The vinyl ester compositions of the present invention contain styrylazagroups and are derived by reaction of epoxidized hydroxystyrylazacompounds with a mono-olefinically unsaturated monocarboxylic acid. Theinvention consists of the vinyl esters and the vinyl ester plus solventand/or copolymerizable vinyl monomer formulations, whether or not cured.

SUMMARY OF THE INVENTION

The present invention pertains to vinyl ester compositions containingstyrylaza groups. Said compositions are prepared by reacting (a) apolyepoxide of a substituted hydroxystyrylaza compound with (b) fromabout 0.75 to about 1, preferably from about 0.9 to about 1, mole of amonounsaturated monocarboxylic acid or mixture of monounsaturatedmonocarboxylic acids per mole of epoxide. The process of making thecompositions is carried out in the presence of from zero to about 2,preferably 0.01 to about 0.5 percent by weight of a suitableesterification catalyst and, optionally, one or more organic solventsinert to the other reactants.

Another aspect of the present invention pertains to the productresulting from curing the aforementioned vinyl esters containingstyrylaza groups.

Another aspect of the present invention pertains to a polymerizablemixture of

(A) at least one of the aforementioned vinyl ester compositionscontaining styrylaza groups and

(B) at least one material selected from

(1) copolymerizable ethylenically unsaturated monomers;

(2) vinyl ester compositions resulting from reacting (a) an epoxy resinrepresented by formulas VIII, IX, X, or XI a mixture of such epoxyresins and (b) at least one monounsaturated monocarboxylic acid;

(3) styryl pyridines and/or prepolymers or polymers thereof;

(4) vinyl styryl pyridines and/or prepolymers or polymers thereof;

(5) alkenylphenyl cyanates;

(6) dicyanates and/or polycyanates;

(7) bismaleimides and/or polymaleimides;

(8) eposy resins;

(9) alkenylphenol capped styryl pyridines and/or prepolymers or polymersthereof;

(10) allyl styryl pyridines and/or prepolymers or polymers thereof;

(11) styryl pyridine cyanates and/or prepolymers or polymers thereof;

(12) furan capped styryl pyridines and/or prepolymers or polymersthereof;

(13) alkenylphenyl glycidyl ether capped hydroxystyryl pyridines and/orprepolymers or polymers thereof;

(14) mixtures thereof in any proportion and combination.

Another aspect of the present invention pertains to polymers and/orcured products of the aforementioned polymerizable and/or curablemixtures.

DETAILED DESCRIPTION OF THE INVENTION

Suitable epoxidized substituted hydroxystyrylaza compounds which can beemployed to prepare the vinyl esters include, for example, thoserepresented by the formulas: ##STR2## wherein each Q is independentlyC-R or N and when Q is C-R, m is 3, when Q is N, m is 2; each R isindependently hydrogen, a halogen, preferably chlorine or bromine, ahydrocarbyl or hydrocarbyloxy group having from 1 to about 20,preferably from 1 to about 4 carbon atoms, nitro, nitroso, nitrile,##STR3## allyl or a methallyl group; E is a hydrocarbyl group havingfrom 1 to about 20 carbon atoms with the proviso that the R groups orthoor para to the glycidyl ether linkage may not be hydrogen; each q has avalue from 0 to about 50; and each R¹ is independently hydrogen or ahydrocarbyl group having from 1 to about 4 carbon atoms.

It is to be understood that in addition to the structures represented byFormulas I and II that minor amounts of other structures may be present.Typical of the minor structures present is that resulting from theaddition of a methyl group of a methylated azine compound to the styryldouble bond. This type of addition product is described by Clavreul andBloch in Makromol. Chem., 188, pp. 47-65 (1987).

Particularly suitable epoxidized substituted hydroxystyrylaza compoundsinclude, for example, the diglycidyl ethers of2,6-(3,5-dimethyl-4-hydroxystyryl) pyridine;2,4-(3,5-dimethyl-4-hydroxystyryl) pyridine;2,6-(3,5-dimethyl-2-hydroxystyryl) pyridine;2,6-(2,3,5,6-tetramethyl-4-hydroxystyryl) pyridine;2,6-(3,5-dibromo-4-hydroxystyryl) pyridine;2,6-(3,5-dimethoxy-4-hydroxystyryl) pyridine;2,6-(3,5-dimethyl-2,6-dibromo-4-hydroxystyryl) pyridine;2,6-(3,5-diethyl-4-hydroxylstyryl) pyridine;2,6-(3,5-diallyl-4-hydroxylstyryl) pyridine;2,6-(3-methyl-5-tert-butyl-4-hydroxystyryl) pyridine;2,6-(3-methyl-5-nitro-4-hydroxystyryl) pyridine;2,6-(3-methyl-5-cyano-4-hydroxystyryl) pyridine;2,6-(3,5-dimethyl-4-hydroxystyryl) pyrazine and the triglycidyl ethersof 2,4,6-(3,5-dimethyl-4-hydroxystyryl) pyridine;2,4,6-(3,5-dimethyl-2-hydroxystyryl) pyridine, mixtures thereof and thelike.

Suitable olefinically unsaturated monocarboxylic acids for reaction withthe epoxidized substituted hydroxystyrylaza compounds include, forexample, acrylic acid, methacrylic acid, cyanoacrylic acid, crotonicacid, α-phenylacrylic acid, methoxyacrylic acid, monomethyl ester ofmaleic acid, monomethyl ester of fumaric acid, mixtures thereof and thelike. Methacrylic acid is a most preferred monounsaturatedmonocarboxylic acid.

Suitable esterification catalysts which are optionally used in thereaction of one or more epoxidized substituted hydroxystyrylazacompounds and one or more monounsaturated monocarboxylic acids are wellknown in the prior art. Chromium trichloride,tris(dimethylaminoethyl)phenol and ethyltriphenyl phosphoniumacetate.acetic acid complex are most preferred as the catalysts. Aquantity of from about 0.01 to about 2 percent by weight has been foundto be a suitable quantity of catalyst with concentrations of 0.1 toabout 0.3 weight percent of the total reactants used being mostpreferred.

A suitable process inhibitor is typically used in the reaction betweenthe epoxidized substituted hydroxystyrylaza compound and amonounsaturated monocarboxylic acid to prevent gelation(homopolymerization of the vinyl ester and/or copolymerization of thevinyl ester with unreacted monounsaturated monocarboxylic acid).Hydroquinone activated with air is a most preferred inhibitor atconcentrations of from about 100 ppm to about 500 ppm based on theweight of the total reactants used.

The reaction to produce the vinyl ester is usually conducted at atemperature of from about 50° C. to about 125° C., preferably from about80° C. to about 120° C. for from about 30 minutes to about 720 minutes,preferably from about 90 to about 240 minutes. Although reaction timesand reaction temperatures can vary substantially, most preferred vinylester compositions are obtained by reacting to a specific conversion,typically 1.5 to 0.25 percent epoxide.

The reaction to produce the vinyl ester is optionally conducted in oneor more organic solvents inert to the other reactants. The term inert asapplied to the organic solvent means that little, if any reactionbetween the epoxidized substituted hydroxystyrylaza compound, themonounsaturated monocarboxylic acid or the vinyl ester thereof occursunder the reaction conditions employed. Typical of the inert organicsolvents are the aliphatic ketones, such as methylisobutyl ketone, thechlorinated aliphatics, such as perchloroethylene, the aromatichydrocarbons, such as toluene and the vinyl aromatic monomers, such asstyrene.

According to the present invention, the curing of the vinyl estercompositions is effected by the application of heat and/or pressure,optionally in the presence of a free radical forming catalyst. Catalyststhat may be used for the curing (polymerization) are preferably theperoxide catalysts, such as benzoyl peroxide, lauroyl peroxide, t-butylhydroperoxide, t-butylperbenzoate, methylethylketone peroxide, potassiumpersulfate and the like. The amount of the catalyst added willpreferably vary from 0.1 to about 2 percent by weight. Temperaturesemployed may vary over a considerable range but usually are in the rangeof 5° C. to 250° C.

Additionally, more rapid curing of the thermosetting vinyl estercompositions may be accomplished by the addition of accelerating agentssuch as lead, vanadium or cobalt naphthenate, N,N-dimethylaniline andthe like, usually in concentrations ranging from about 0.01 to about 2percent by weight.

Styryl pyridine prepolymers and/or polystyryl pyridines which can beemployed to prepare the polymerizable mixtures of the present inventioninclude those described by Ropars et al in U.S. Pat. Nos. 3,994,862 and4,525,573; Melassine et al in U.S. Pat. No. 4,163,740 and Chevallier inU.S. Pat. No. 4,540,770 which are incorporated herein by reference.

Suitable vinyl esters which can be employed herein include thosedescribed by Bearden in U.S. Pat. No. 3,367,992, Bowen in U.S. Pat. Nos.3,006,112 and 3,179,623, Fekete in U.S. Pat. Nos. 3,301,743 and3,256,226 which are incorporated herein by reference.

Suitable vinyl styryl pyridines and/or vinyl polystyryl pyridines whichcan be employed herein include those described by Ratto el al in U.S.Pat. No. 4,362,860; by Peake in U.S. Pat. No. 4,471,107; and by Ming-taet al in Technology Vectors, Vol. 29, pages 1034-1042 (1984) publishedby the Society for the Advancement of Material and Process Engineeringwhich are incorporated herein by reference. A specific preparation of avinyl polystyryl pyridine is taught by Hefner, Jr. in U.S. Pat. No.4,578,439 which is additionally incorporated herein by reference.

Suitable alkenylphenyl cyanates which can be employed herein include,for example, those represented by the formula ##STR4## wherein each R²,R³ and R⁴ is independently hydrogen or a hydrocarbyl group having from 1to about 3 carbon atoms and each X is independently hydrogen, ahydrocarbyl or hydrocarbyloxy group having from 1 to about 4 carbonatoms, chlorine or bromine or a phenyl group.

Particularly suitable alkenylphenyl cyanates include, for example,p-isopropenylphenyl cyanate, p-vinylphenyl cyanate, m-vinylphenylcyanate, methyl-p-isopropenylphenyl cyanate,3-chloro-4-isopropenylphenyl cyanate, o-allylphenyl cyanate,p-allylphenyl cyanate mixtures thereof and the like. It is mostpreferred that the alkenylphenyl cyanate be substantially free ofdimeric and/or oligomeric components although it is operable to use analkenylphenyl cyanate containing substantial (up to 90 percent byweight) dimeric and/or oligomeric components. Said components are formedduring the cyanation reaction of an alkenylphenol containing thecorresponding dimeric diphenols and/or oligomeric polyphenols. Aspecific preparation of p-isopropenylphenyl cyanate is taught by Hefner,Jr. in U.S Pat. No. 4,578,439 which is incorporated herein by reference.

Suitable aromatic dicyanates (polycyanates) which can be employed hereininclude, for example, those represented by the formulas ##STR5## whereineach A is independently an alkylene group having from 1 to about 10carbon atoms, preferably from 1 to about 4 carbon atoms, --O--, ##STR6##--S--, --S--S--, ##STR7## --SO₂ --; each A' is independently an alkylenegroup having from 1 to about 6, preferably from 1 to about 4 carbonatoms or a ##STR8## group; each Z is independently hydrogen, ahydrocarbyl or hydrocarbyloxy group having from 1 to about 10,preferably 1 to about 4 carbon atoms, a halogen, preferably chlorine orbromide, a phenyl group, or a --O--C.tbd.N group; Z' is independentlyhydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about10, preferably 1 to about 4 carbon atoms, a halogen, preferably chlorineor bromine, or a phenyl group; p has a value of from zero to about 10,preferably from zero to 3; n has a value of zero or 1; m has a valuefrom zero to about 100, preferably from zero to about 30; n" has a valueof from about 0.001 to about 6, preferably from about 0.01 to about 3; zhas a value of 4, and z' has a value of 3.

Particularly suitable aromatic dicyanates (polycyanates) which can beemployed herein include bisphenol A dicyanate; the dicyanates of4,4'-dihydroxydiphenyl oxide, resorcinol, 4,4'-thiodiphenol,4,4'-sulfonydiphenol, 3,3'5,5'-tetrabromobisphenol A,2,2'6,6'-tetrabromobisphenol A, 3-phenylbisphenol A,4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl,2,2',4,4'-tetrahydroxydiphenyl methane,2,2',6,6'-tetramethyl-3,3',5,5'-tetrabromobisphenol A,3,3'-dimethoxybisphenol A; ##STR9## the tricyanate oftris(hydroxyphenyl)methane, the polycyanate of a phenolformaldehydecondensation product (novolac), the polycyanate of a dicyclopentadieneand phenol condensation product and the like. The aromatic polycyanatesmay be used either alone or in any combination. A specific preparationof bisphenol A dicyanate is taught by Hefner, Jr., in U.S. Pat. No.4,578,439 which is incorporated herein by reference.

Suitable epoxy resins include materials having an average of more thanone vicinal epoxide group per molecule such as, for example, theglycidyl ethers represented by the formulas ##STR10## wherein A¹ isindependently an alkylene group having from 1 to about 10 carbon atoms,preferably from 1 to about 4 carbon atoms, --O--, ##STR11## --S--,--S--S--, ##STR12## --SO₂ --, A', Z', R¹, n, n", z, z" and p are ashereinbefore defined and n' has a value of from about zero to about 30,preferably from about zero to about 5.

Particularly suitable polyepoxides which can be employed herein include,for example, the diglycidyl ethers of resorcinol, bisphenol A,4,4'-dihydroxy-biphenyl, 4,4'-dihydroxydiphenyl methane,3,3',5,5'-tetrabromobisphenol A, the triglycidyl ether oftris(hydroxyphenyl)methane, the polyglycidyl ether of aphenolformaldehyde condensation product (novolac), the polyglycidylether of dicyclopentadiene and phenol condensation product and the like.The polyepoxides can be used either alone or in combination.

The aforementioned epoxy resins can be prepared by reaction of adiphenol or polyphenol with an epihalohydrin and a basic actingmaterial. Said reaction generally involves two distinct steps: couplingreaction of the epihalohydrin and diphenol or polyphenol to provide ahalohydrin intermediate and dehydrohalogenation reaction of thehalohydrin intermediate to provide the glycidyl ether product. Suitablecatalysts and reaction conditions for preparing polyepoxides aredescribed in the Handbook of Epoxy Resins by Lee and Neville,McGraw-Hill (1967) which is incorporated herein by reference.

Particularly preferred epoxy resins include, for example, styrylpyridine epoxy resins described by Yan et al in "Styryl-Pyridine BasedEpoxy Resins: Synthesis and Characterization" in Organic Coatings andApplied Polymer Science Proceedings, Vol. 46, pp. 482-488 (1982)published by American Chemical Society which is incorporated herein byreference.

Suitable alkenylphenol capped styryl pyridines and/or alkenylphenolcapped polystyryl pyridines which can be employed herein include thoseprepared by reacting a di- or polymethyl pyridine compound with anaromatic di- or polyaldehyde. The resultant product is then reacted withan alkenylphenol represented by the formula III. Preparation of saidalkenylphenol capped styryl pyridines is taught by LaTulip in U.S. Pat.No. 4,500,690 which is incorporated herein by reference.

Suitable bismaleimides (polymaleimides) which can be employed hereininclude, for example, those represented by the formulas ##STR13##wherein R¹, n and A are as hereinbefore defined; Q' is an alkylene grouphaving from 2 to about 12 carbon atoms and m¹ has a value of 0.01 toabout 10.

Particularly suitable bismaleimides (polymaleimides) which can beemployed herein include, for example, N,N'-ethylenebismaleimide,N,N'-ethylenebis(2-methylmaleimide), N,N'-hexamethylenebismaleimide,N,N'-(oxydi-p-phenylene)bismaleimide,N,N'-(methylenedi-p-phenylene)bismaleimide,N,N'-(thiodi-p-phenylene)bismaleimide,N,N'-(sulfonyldi-m-phenylene)bismaleimide,N,N'-(isopropylidenedi-p-phenylene)bismaleimide, polymethylenepolyphenylene polymaleimides and the like. The bismaleimides(polymaleimides) may be used either alone or in any combination.

The bismaleimides (polymaleimides) can be prepared by reacting astoichiometric quantity of a maleic anhydride per amine group with adiamine (polyamine) in the presence of a suitable solvent.

Preparation of bismaleimides (polymaleimides) is disclosed by Arnold etal in U.S. Pat. No. 2,462,835 and by Searle in U.S. Pat. No. 2,444,536which are incorporated herein by reference. A specific preparation ofN,N'-(methylenedi-p-phenylene)bismaleimide is taught by Hefner, Jr. inU.S. Pat. No. 4,578,439 which is incorporated herein by reference.

Suitable styryl pyridine cyanates and/or polystyryl pyridine cyanateswhich can be employed herein include those prepared by reacting ahydroxy styryl pyridine and/or hydroxy polystyryl pyridine with acyanogen halide in the presence of a base or basic-acting substance.Preparation of said styryl pyridine cyanates is taught by Hefner, Jr. inU.S. Pat. No. 4,578,439 which is incorporated herein by reference.

Suitable allyl styryl pyridines and/or allyl polystyryl pyridines whichcan be employed herein include those prepared by reacting an allylatingagent such as an allyl halide or allyl methyl carbonate with ahydroxystyryl pyridine and/or a hydroxy polystyryl pyridine. Preparationof said allyl styryl pyridines is taught by Hefner, Jr. in U.S. Pat. No.4,540,745 which is incorporated herein by reference.

Suitable alkenylphenyl glycidyl ether capped hydroxystyryl pyridinesand/or alkenylphenyl glycidyl ether capped hydroxypolystyryl pyridineswhich can be employed herein include those prepared by reacting aalkenylphenyl glycidyl ether with a hydroxystyryl pyridine and/or ahydroxypolystyryl pyridine. Preparation of said alkenylphenyl glycidylether capped hydroxystyryl pyridines is taught by Hefner, Jr. in U.S.Pat. No. 4,539,377 which is incorporated herein by reference.

Suitable furan capped styryl pyridines and/or furan capped polystyrylpyridines which can be employed herein are described in Ser. No. 848,100filed Apr. 4, 1986, now U.S. Pat. No. 4,736,035 which is incorporatedherein by reference.

Suitable copolymerizable ethylenically unsaturated monomers include thevinyl aromatic compounds such as styrene, α-methylstyrenes,vinyltoluenes, halogenated styrenes, t-butylstyrenes, divinylbenzenes,and the like. Other suitable monomers include the methyl, ethyl,isopropyl, octyl, etc., esters of acrylic or methacrylic acid, vinylacetate, diallyl maleate, dimethallyl fumarate, acidic monomers such asacrylic acid, methacrylic acid, crotonic acid and amide monomers such asacrylamide, N-alkyl acrylamides and the like and mixtures thereof. Allylmonomers such as diallylphthalate, triallylisocyanurate, and the likemay also be used.

Preferred copolymerizable monomers are styrene, vinyltoluene, ortho-,meta- and para-halostyrenes, vinylnaphthalenes, the variousα-substituted styrenes as well as the various di-, tri- andtetra-halostyrenes, and acrylic, methacrylic and crotonic acid esterswhich include both the saturated alcohol esters and the hydroxylalkylesters.

If an inert solvent, other than one containing polymerizable ethylenicunsaturation is used to prepare the vinyl ester product, it ispreferably removed, for example, via distillation under vacuum, prior toaddition of one or more of the aforesaid polymerizable materials. Forcertain end uses, such as coating or impregnating a fibrousreinforcement, the presence of an inert solvent is desirable as avehicle for the polymerizable mixture.

Curing of the polymerizable mixtures varies as a function of the amountand type of each component present to comprise said mixture. Generally,the application of heat and/or pressure optionally in the presence ofone or more catalysts suitable for curing the curable functionalmoieties provided by the components of the mixture and defined in theincorporated cited prior art produce a cured product. As a specificexample, (A) vinyl esters containing styrylaza groups and one or more of(B-1) copolymerizable ethylenically unsaturated monomers and/or (B-2)vinyl ester compositions resulting from reacting one or more epoxyresins of formulas VIII, IX, X, XI and one or more monounsaturatedmonocarboxylic acids are cured using the previously described method forthe vinyl ester containing styrylaza groups.

The vinyl esters containing styrylaza groups and polymerizable mixturesthereof are useful to make laminates, castings, coatings, and the like.The laminates are made by mixing into the vinyl ester or polymerizablemixture containing the vinyl ester a known amount of one or morecatalysts and/or accelerators and adding this mixture to a suitablefibrous reinforcement such as asbestos fibers, carbon fibers, fibrousglass or inorganic fibers. The vinyl ester or polymerizable mixture canbe rolled, sprayed or impregnated into the fibrous reinforcement, suchas fibrous glass. When fibrous glass is used, it can be in any form suchas chopped strands, filaments, glass ribbons, glass yarns or reinforcingmats.

The vinyl ester or polymerizable mixture may be compounded withsolvents, pigments, low profile additives, fillers, flow modifiers orother resinous products and cured to form useful coatings in a mannerwell known in the art.

The following examples are illustrative of the invention, but are not tobe construed as to limiting the scope thereof in any manner.

EXAMPLE 1 A. Synthesis of 2,6-(3,5-dimethyl-4-hydroxystyryl)pyridine

107 g of 2,6-lutidine (1 mole), 375 g of3,5-dimethyl-4-hydroxybenzaldehyde (2.5 moles), 510 g of aceticanhydride (5 moles) and 300.2 g of acetic acid (5 moles) were placed ina 2-liter round bottom flask equipped with a magnetic stirrer, nitrogenpad, thermometer and reflux condenser. The flask was heated to 140° C.for five days. The flask was then cooled to room temperature andequipped with a simple distillation head. The solution was distilled toremove the acetic acid and acetic anhydride. The remaining materialafter cooling to room temperature was a light brown solid. The solid wasthen washed with 1000 ml of methanol and filtered resulting in a whitesolid that was analyzed by nuclear magnetic resonance spectroscopy (NMR)and demonstrated to be 2,6-di(3,5-dimethyl-4-acetoxystyryl)pyridine. Thewhite solid, 200 ml of methanol, 1000 ml of water and 88.0 g of NaOH(2.2 moles) were placed in a 2-liter round bottom flask equipped thesame as above and heated to 70° C. with stirring for 24 hours. The flaskwas then cooled to room temperature and equipped with a distillationhead. The flask was heated to distill off the methanol and leave thewater soluble sodium salt. The aqueous solution was then acidified withHCl causing a pale yellow solid to drop out. The solid was filtered anddried under vacuum at 110° C. for 2 hours. The material was analyzed byNMR and differential scanning calorimetry (DSC). The NMR analysisconfirmed the product structure. The DSC showed a distinct melting pointat 207° C. (endotherm) with no exotherms noted.

B. Synthesis of Epoxy Resin of2,6-(3,5-dimethyl-4-hydroxystyryl)pyridine

A portion (185.73 grams, 1.0 hydroxyl equivalent) of the substitutedhydroxystyrylpyridine from A above, epichlorohydrin (5.0 moles, 462.65grams), isopropanol (35% by weight of epichlorohydrin used, 249.12grams) and water (8% by weight of epichlorohydrin used, 40.23 grams)were added to a reactor and stirred under a nitrogen atmosphere at 50°C. until a fine suspension was formed. At this time, dropwise additionof sodium hydroxide (1.8 moles, 72.0 grams) solution in water (288.0grams) commenced and was completed over the next 45 minutes and at arate so as to maintain the reaction temperature between 50° and 52° C.Fifteen minutes after the addition of sodium hydroxide solution, asecond solution of sodium hydroxide (0.8 mole, 32.0 grams) in water(128.0 grams) was added dropwise to the reactor over the next 20 minutesso as to maintain the reaction temperature at 50° C. After fifteenminutes of post reaction between 50° and 53° C., the reactor was cooledover a 14 minute period to 40° C. then an initial water wash (750 grams)was added to the reactor and the contents were transferred to aseparatory funnel. The water wash layer was separated and discardedwhile the organic layer was added back into the separatory funnel with asecond water wash (750 grams) and epichlorohydrin (250 grams). The waterwash layer was separated and discarded while the organic layer was addedback into the separatory funnel with a final water wash (500 grams). Therecovered organic layer was stripped of solvents by rotary evaporationat 80° C. for 120 minutes under vacuum. The epoxy resin was recovered(234.9 grams) as a light gray colored solid. Epoxide titration (withcorrection for response provided by the substitutedhydroxystyrylpyridine starting reactant) revealed the presence of 16.99%epoxide. Nuclear magnetic resonance spectroscopic analysis of a portionof the epoxy resin demonstrated complete conversion of the phenolichydroxyl groups to glycidyl ether groups. Differential scanningcalorimetry revealed a distinct melting point endotherm at 158° C.followed by an exotherm at 315° C.

C. Methacrylation of the Epoxy Resin of2,6-(3,5-dimethyl-4-hydroxystyryl)pyridine

A portion (50.0 grams) of the epoxy resin of2,6-(3,5-dimethyl-4-hydroxystyryl)pyridine from B above andmethylisobutyl ketone (100 grams) were added to a reactor and heated to90° C. Hydroquinone (0.0266 gram) then methacrylic acid (16.48 grams)were sequentially added then stirring and sparging with air (0.5 literper minute) were started. After three minutes at the 90° C. reactiontemperature, 33.33 percent aqueous chromium trichloride catalyst (0.0625gram) was added and the temperature controller was set at 110° C. andthis temperature was achieved two minutes later. After two minutes atthe 110° C. reaction temperature, the temperature controller was set at115° C. and this temperature was achieved two minutes later. After 121minutes at the 115° C. reaction temperature, titration of a sample ofthe vinyl ester demonstrated the presence of 0.67 percent epoxide (withcorrection for response provided by the substitutedhydroxystyrylpyridine starting reactant and solvent dilution). Infraredspectrophotometric analysis of a solvent free film sample of the vinylester demonstrated the presence of the expected carboxylic acid esterfunctionality (1721 cm⁻¹). The vinyl ester was recovered in essentiallyquantitative yield as a transparent amber solution inmethylisobutylketone.

EXAMPLE 2 A. Differential Scanning Calorimetry of Methacrylation Productof Epoxy Resin of 2,6-(3,5-dimethyl-4-hydroxystyryl)pyridine

Differential scanning calorimetry (DSC) of a portion of the solvent freevinyl ester of Example 1C (12.3 milligrams) was completed using a rateof heat increase of 10° C. per minute from 30° C. to 350° C. undernitrogen gas flowing at a rate of 35 cc per minute. The vinyl estersample was prepared by allowing a solution cast film on mylar todevolatilize at 25° C. for 48 hours. A minor exotherm at 94° C. wasfollowed by two larger exotherms of 168° C. and 290° C., respectively.

B. Thermal Mechanical Analysis (Expansion Mode) of Cured MethacrylationProduct of Epoxy Resin of 2,6-(3,5-dimethyl-4-hydroxystyryl)pyridine

Thermal mechanical analysis (TMA) of a portion of the vinyl ester ofExample 1C devolatilized and cured at 177° C. for 1.5 hours wascompleted using a rate of heat increase of 10° C. per minute from 50° C.to 300° C. A midpoint glass transition temperature (Tg) of 165.5° C. wasobserved. An additional post cure for 2 hours at 220° C. produced anincrease in Tg to 170.6° C.

C. Thermogravimetric Analysis (TGA) of Cured Methacrylation Product ofEpoxy Resin of 2,6-(3,5-dimethyl-4-hydroxystyryl)pyridine

Thermogravimetric analysis (TGA) of a portion of the vinyl ester ofExample 1C devolatilized and cured at 177° C. for 1.5 hours wascompleted using a rate of heat increase of 10° C. per minute from 50° C.to 800° C. under nitrogen flowing at a rate of 35 cc per minute. A 5percent weight loss was observed at a temperature of 300° C. The weightpercent of material remaining at the 800° C. temperature was 26.5percent.

A second portion of cured vinyl ester of Example 1C was analyzed by TGAutilizing the aforementioned conditions except for a change to an airatmosphere instead of nitrogen. A 5 percent weight loss was observed ata temperature of 311° C. The weight percent material remaining at the800° C. temperature was 3.2 percent.

EXAMPLE 3 A. Methacrylation of Epoxy Resin of2,6-(3,5-dimethyl-4-hydroxystyryl)pyridine in Styrene

A portion (44.5 grams) of the epoxy resin of2,6-(3,5-dimethyl-4-hydroxystyryl)pyridine from Example 1B and styrene(39.45 grams) containing 50 ppm t-butylcatechol were added to a reactorand heated to 90° C. Hydroquinone (0.0237 gram) then methacrylic acid(14.67 grams) were sequentially added then stirring and sparging withair (0.5 liter per minute) were started. After three minutes at the 90°C. reaction temperature, 33.33 percent aqueous chromium trichloridecatalyst (0.0556 gram) was added the temperature controller was set at110° C. and this temperature was achieved two minutes later. After twominutes at the 110° C. reaction temperature, the temperature controllerwas set at 115° C. and this temperature was achieved one minute later.After 120 minutes at the 115° C. reaction temperature, titration of asample of the vinyl ester demonstrated the presence of 1.08 percentepoxide (with correction for response provided by the substitutedhydroxystyrylpyridine starting reactant and dilution by styrene). Thevinyl ester solution in styrene was recovered (97.4 grams) as atransparent amber liquid.

B. Mechanical Properties of Cured Methacrylation Product of Epoxy Resinof 2,6-(3,5-dimethyl-4-hydroxystyryl)pyridine

The styrenated vinyl ester resin from A above was used to prepare aclear, unfilled, 1/8 inch casting using a cure system of 2.0 percent byweight methylethylketone peroxide and 0.2 percent by weight cobaltnaphthenate (6.0 percent) at room temperature (25° C.). Post curing wascompleted twelve hours after the room temperature cure exotherm subsidedusing a temperature of 100° C. for 2 hours then 150° C. for 2 hours.Mechanical properties of tensile (4) and flexural (2) test pieces weredetermined using an Instron machine with standard test methods (ASTMD-638 and ASTM D-790). Differential scanning calorimetry (DSC) of a 12milligram portion of the clear, unfilled casting was completed using themethod of Example 2A. The average Barcol hardness value is on the 934-1scale. The results are given in Table I.

                  TABLE I                                                         ______________________________________                                        Average Barcol Hardness 43                                                    Tensile Strength, psi   12,126                                                Elongation, %           6.05                                                  Flexural Strength, psi  20,798                                                Flexural Modulus, psi   480,000                                               Midpoint Glass Transition                                                                             152.7                                                 Temperature, °C.                                                       ______________________________________                                    

COMPARATIVE EXPERIMENT 1 Attempted Methacrylation of a Diglycidyl Etherof Bisphenol A in Styrene

A portion (44.5 grams) of a diglycidyl ether of bisphenol A having anepoxide equivalent weight (EEW) of 181.8 and styrene (43.28 grams)containing 50 ppm t-butylcatechol were added to a reactor and heated to90° C. Hydroquinone (0.0260 gram) then methacrylic acid (20.42 grams)were sequentially added then stirring and sparging with air (0.5 literper minute) were started. After three minutes at the 90° C. reactiontemperature, 33.33 percent aqueous chromium trichloride catalyst (0.0556gram) was added and the temperature controller was set at 110° C. andthis temperature was achieved three minutes later. After two minutes at110° C. reaction temperature, the temperature controller was set at 115°C. and this temperature was achieved one minute later. After 137 minutesat the 115° C. reaction temperature, titration of a sample of thereaction product demonstrated the presence of 6.17 percent epoxide (withcorrection for dilution by styrene). After 289 minutes at the 115° C.reaction temperature, titration of a sample of the reaction productdemonstrated the presence of 3.02 percent epoxide. After an additional30 minutes of reaction, the reaction product gelled to a rigid mass andwas discarded.

We claim:
 1. A polymerizable mixture comprising(I) the vinyl ester resincomposition prepared by reacting(A) a polyepoxide of a thermostablehydroxystyrylaza compound wherein said hydroxystyrylaza compound isprepared by reacting(1) one or more mono hydroxy aromatic aldehydeswherein the ortho and para positions from the hydroxy group having noaldehyde groups are substituted by groups inert to condensation withalkyl azines, and (2) one or more methylated azine compounds having theformula ##STR14## where Q is N or C-R, and each R is independentlyhydrogen, a halogen, a hydrocarbyl or hydrocarbyloxy group having from 1to 20 carbon atoms, nitro, nitroso, nitrile, ##STR15## allyl or amethallyl group; E is a hydrocarbyl group having from 1 to about 20carbon atoms with the proviso that the total number of methyl groups(R=--CH₃) substituted on the ring is in the range from 2-4 and whereinsaid polyepoxy compound has one of the following formulas ##STR16##wherein Q is independently C-R or N and when Q is C-R, m is 3, when Q isN, m is 2; each R is independently hydrogen, a halogen, a hydrocarbyl orhydrocarbyloxy group having from 1 to about 20 carbon atoms, nitro,nitroso, nitrile, ##STR17## allyl or a methallyl group; E is ahydrocarbyl group having from 1 to about 20 carbon atoms with theproviso that the R groups ortho or para to the glycidyl ether linkagemay not be hydrogen; q has a value from 0 to about 50; and R¹ isindependently hydrogen or a hydrocarbyl group having from 1 to about 4carbon atoms with (B) about 0.75 to about 1.0 mole of one or moremono-olefinically unsaturated monocarboxylic acids per mole of epoxide;and (II) one or more members of the group consisting of(A) ethylenicallyunsaturated monomers, (B) vinyl ester compositions derived from (1) oneor more epoxy resins represented by the following formulas VIII, IX, Xor XI ##STR18## wherein A¹ is independently an alkylene group havingfrom 1 to about 10 carbon atoms, --O--, --CO--, --S--, --S--S--, --SO--,--SO₂ --; each A' is independently an alkylene group having from 1 toabout 6 carbon atoms or a ##STR19## group; Z' is independently hydrogen,a hydrocarbyl or hydrocarbyloxy group having from 1 to about 10 carbonatoms, a halogen, or a phenyl group; each R¹ is independently hydrogenor a hydrocarbyl group having from 1 to about 4 carbon atoms; n has avalue of zero or 1; n' has a value of from about zero to about 30; n"has a value from about 0.001 to about 6; p has a value from zero toabout 10; z has a value of 4; and z' has a value of 3; and (2) at leastone mono-olefinically unsaturated monocarboxylic acid, (C) styrylpyridines, and/or their prepolymers or polymers, (D) vinyl styrylpyridines, and/or their prepolymers or polymers, (E) alkenylphenylcyanates, (F) dicyanates and/or polycyanates, (G) bismaleimides and/orpolymaleimides, (H) epoxy resins, (I) alkenylphenol capped styrylpyridines and/or their prepolymers or polymers, (J) allyl styrylpyridines and/or their prepolymers or polymers, (K) styryl pyridinecyanates and/or their prepolmers or polymers, (L) furan capped styrylpyridines and/or their prepolymers or polymers, and (M) alkenylphenylglycidyl ether capped hydroxystyryl pyridines and/or their prepolymersor polymers.
 2. The cured composition of claim 1.